Metal complexes and methods of making same



United States Pat ent METAL COMPLEXES AND METHODS OF MAKING SAME NoDrawing. Application November 3, 1952, Serial No. 318,528

26 Claims. (Cl. 260-504) This application is a continuation-in-part ofour co- I pending application Serial No. 216,101, filed March 16,

1951, and is a continuation-in-part also of our related I co-pendingapplications Serial No. 216,102, now Patent No. 2,617,049; 216,103, nowPatent No. 2,616,924; 224,458, now Patent No. 2,695,910; 263,961, nowPatent No. 2,616,925; 263,962, now Patent No. 2,616,911; 263,963, nowPatent No. 2,616,904; 276,461, now abandoned; and 276,462, now PatentNo. 2,616,905.

In our aforesaid parent application Serial No. 216,101, there isdisclosed the process of producing certain novel organic salt complexesand the novel products resulting from such processes.

The present invention is concerned with the use of certain features ofthe process to which our said parent applications relate for theproduction of complexes which have particular properties which suit themfor particular uses.

From the processes contemplated by our said parent applications, it ispossible to produce organic metal complexes in which the metal contentthereof is derived at least in part from the metal present in the normalsalt of the starting acid, and metal contributed to the complex by aninorganic basically reacting material; and, optionally, according to theprocesses of our said parent applications, metal in the complex may bederived from the so-called promoter material.

The present invention is concerned with a process wherein the metal isder'ved from only two sources: specifically, (1) from the normal salt ofthe starting acid; and (2) from the so-called promoter material. Thepresent process is characterized further in that the reaction mass whichthus includes the starting acid, or, more particularly, its normal salt,and the metal containing promoter material is subjected to an acidtreatment step utilizing for that purpose an acidic material which has2,777,874 Patented Jan. 15, 1957 tion there will be given numerousexamples of starting acids and numerous examples of metals. As indicatedabove, it is within the contemplation of our invention to utilizemixtures of diiferent acids as well as mixtures of different metals. Thevarious combinations of reaction mass components which may thus beutilized include, for example, the following:

1. A single acid entirely neutralized with a single metal employed inconjunction with a promoter containing the same metal;

2. A single acid in which different portions thereof are neutralized bydifferent metals employed in conjunction with a promoter material w chmay contain one or more metals, as by having a plurality of differentmetals associated with the same kind of anions, or a plurality ofdifferent kinds of anions associated with the same type cation.

From the foregoing, it will be apparent that there are many possibleways in which a plurality of starting acid anions and a plurality ofmetals may be included in the resultant complex. At this point, itshould be observed also that, whereas all of the metal in the complexother than that derived from the normal salt of the starting acid iscontributed to the complex by the promoter material used, it isnevertheless within the contemplation of our inventionto use along withsuch metal containing promoter materials, promoters which are metalfree. It is also within the contemplation of our invention to use, inlieu of the metal containing promoter, an admixture of metal-freepromoter plus an amount of free inorganic metal base up to but notgreater than that amount required stoichiometrically to form the salt ofthe metalan ionization constant greater than the ionization constant ofthe organic acid reacting compound from which the anion of the promotermaterial is derived.

Where reference is made throughout this specification and in theattendant claims to the starting acid, or the acidic material, we shallpresently give examples. We intend to include in the product of a singlecomplex material, or product, one or more of different such acids orthe'normal salts, since as will be presently explained, there areunusual advantages to be derived from the use of an admixture ofdifferent starting acids.

When we refer to the fact that the entire metal content of the complexesof this invention are derived from the normal salt of the starting acidsand from the promoter material, it is to be understood that inconfecting the reaction mass, we may use either the starting acid, assuch, together with an amount of basically reacting materialsubstantially equal to that required stoichiometrical- 1y to neutralizethe amount of acids used, or we may utilize the normal metal salt withno free base present in the reaction mass. Throughout the followingdescripfree promoter. This refinement finds particular utility when theinorganic metal base is highly alkaline in nature, for example, thealkali and alkaline earth oxides and hydroxides, particularly bariumoxide and barium hydroxide. The use of some metal-free promoter materialis highly desirable for certain purposes since the complex producedthereby tends to be more truly homogeneous, and the behavior of thereaction mass during the processing is such that the processing iseasier when some metal-free promoter is used.

In the following section of the specification, we shall first list theacidic materials which may thus be used in providing the anion of thenormal metal salt, it being understood, as indicated above, that variouscombinations of such acidic starting metals may be used or their salts.

THE OIL SOLUBLE ACIDIC ORGANIC COM- POUNDS AND/ OR THE SALTS THEREOF asthe aliphatic or aromatic organic acids e. g.', thesulfur acids, thecarboxylic acids, acids of phosphorus, etc.,or the salts of such acids,including the corresponding thio acids of any of the foregoing as wellas mixtures of the same. The aromatic compounds include the monoorpolynuclear typesof the benzenoid and heterocyclic classes; whereas thealiphatic compounds are for example the acyclic and cyloaliphaticcompounds. It is intended that all such compounds be oil soluble forthis invention, and in the preferred instance oil solubility is meantthat the salt of the acidic organic compound will possess a solubilityof at least about 10% in Pennsylvania conventionally refined mineral oilhaving a viscosity of about 150 SUS at F., or what is commonly known asPennsylvania neutral oil.

More specific illustrations of the types of oil-soluble acidic organiccompounds or the salts thereof which can be employed are, for example,

(1) Organic acids in which:

" (alsullur is the acidforming element,'for example:

Organic acids containing the SO:H radical, e. g.:

Sulionic acids Sulfamic acids Thiosulfonic acids Organic acidscontaining the r-S02 radical, e. g.:

Sulfinic acids Thionamic acids Sulienic acids Partial esters ofpolybasic inorganic sulfur acids, e. g.:

Mono-esters of sulfuric acid Mono-esters of sulfurous acid Mono-estersof thiosuliuric acid (b) Selenium is the acid-forming element, forexample:

Selenonic acids Seleninic acids Partial esters of polybasic inorganicselenium acids, e. 3.:

Mono-esters oi selenic acid Mono-esters of selenious acid Tellurim istheacid forming element, for example:

Telluronic acids Tellurinic acids Partial esters of polybasic inorganictellurium acids, 6. g.:

Mono-esters of telluric acid Mono-esters of tellurous acid (d) Carbon isthe acid-forming element for example:

Organic acids containing the G0zl1 radical, e. g.:

Carboxylic acids N-substituted carbamic acid Organic acids containingthe -OXzH radical, where X is either 0 or S and at least one X issulfur, c. g.:

Thiocarboxylic acids N-substituted thiocarbamic acid Seleno-carboxylicacids Telluro-carboxylic acids (e) Nitrogen is the acid-forming element,for example:

Nitrolic acids: R-C (:NOH)NO Nitrosolic acids: R-C (:NOH)NO Nitronicacids: RzCINOOH Nitroic acids: RNO (0H 2 Carbazyllc acids: B-O 2NH)NH2(f) Phosphorus is the acid-forming element, for example: Phosphinicacids; RXP(OH)3-z where z is 1 or 2 Phosphonic acids; RxPO(0H)3-= Wherea: is 1 or 2 Throphosphinic acids; Rx]? (ZH) where a: is 1 or 2, andwhere Z is either O or Sand at least one Z is sulfur Thlophosphomcacids; RXPZ(ZH) where a: is 1 or 2, and where Z is either 0 or S and atleast one Z is sulfur Partial1 esters of polybasic inorganic phosphorusacids, for exarnp e:

Mono-esters of phosphorous acid Mono-esters of thiophosphorous acidsMonoand di-esters of phosphoric acid Monoand di-esters of thiophosphorlcacids Partial esters of pyrophos'phoric acid Partial esters ofpyrophosphorous acid Partial esters of polyphosphoric acids Partialesters of polyphosphorous acids Partial esters of pyrothiophosphoricacids Partial esters of pyrothiophosphorous acids Partial esters ofthlopolyphosphoric acids Partial esters of thiopolyphosphorous acids (0)Arsenlc is the acid-forming element, for example:

Arslnlc acids Arsonic acids Partial esters of polybasic, inorganic,arsenic-derived acids, e. g.:

Mono-esters of arsenious acid Monoand di-esters of arsenic acid (It)Antimony is the acid'iorming element, for example:

Strbonlc acids Partial esters of polybaslc inorganic antimony acids, e.g.:

Mono-esters of antimonous acid Monoand di-esters of antimonic acid (1)Silicon is the acid-forming element, for example:

Sllleonic acids: RSiO 0H Partial esters of sllicic acid Tm rs theacid-forming element, for example: stannonic acids;

n (1:) Lead is the acid-forming element for exam 1e: lurnb sermon), andRPbOOH p 9 mm acids (2) Salts of the organic acids listed under (1).

The salts included under (2) are metal salts and organic salts. Themetal salts include the mono or polyvalent metals, such as the light orheavy metals, or the alkali and alkaline earth metals such as sodium,lithium, potassium, calcium, barium, strontium, magnesium, and otherMahogany sull'onio acids Pctrolatu'm 'sulfonlc 'aclds Substitutedaromatic sulionic acids, e. g.:

Monoand poly-wax substituted naphthalene sulfonic acids MOIIO- 811d Py-wax substituted phenol sulfcnic acids Monoand poly-wax substituteddlphenyl ether sulfonlc acids Monoand poly-wax substituted naphthalenedisulflde sultonic acids Monoand poly-wax substituted 'diphenyl aminesulionlc acids Monoand polyvwax substituted thiophene sulfonic acidsMongand poly-wax substituted alpha-chloronapbthalene sulicnic sex 5N,N-di-wax aniline sullonic acids Fuel oil substitutedlnaphthalcnesullonic acids Fuel oil substituted diphenyl ether sulionic acidsKerosene substituted diphenyl ether sulfonic acids Pctrolatumsubstituted naphthalene sulfonic acids 'Petrolatum substituted phenolsulfonic acids Pctrolatum substituted anthracene sulionlc acidsPetrolatum substituted naphthalene disulfide sulfomcacidsCeryl-diphenylene sulfonic acids Cetyl chloro-benzene sulfonic acidsOetyl-phenol sulfonic acids Cetyl-phcnol disulfide sulfonic acidsOctyl-phenol monosulfide sulfonic acids Di-cetyl thianthrcne sulfouicacids Cetoxy capryl benzene sulfonic acids Di-lauryl chlorophenolsulionic acids Di-lauryl betanaphthol sulfonic acids Trl-laurylphenothioxlne sulfonic acids Di-lauryl rncnohloro diphcnyl ethersulfonio acids Bis-(di-lsobutyl-carbinyl) naphthalene sulionic acidsDl-capryl ultra-naphthalene sullonic acids Tri-capryl benzene sulfonicacids 7 Tri-capryl dlpbenyl sulfide sulionic acids Dl-capryl methylnaphthalene sulfonic acids Di-capryl ortho-phenylphenol sulfonic acidsTetra-capryl meta-terphenyl-sullonlc acids Dl-capryl thiophene sullonicacids Diisobutyl (2,4,5-trichlorobenzyloxy) benzene suliomcacldsp-Oapryl-o-cyclohcxyl phenol sulionic acids Bis-(diisobutyl) naphthalenesulfonic acids Tris-(diisobutyl) anthracene sulfonic acidsBis-(diisobutyl) diphenylcne sulfide sulfonic acids Aliphatic sulfonicacids (acyclic), e. g.:

Parafiin wax sulfonic acids Unsaturated parafiin wax sulfonic acidsHydroxyl-substitutcd parafiin wax sullomc acids Nitroso-substitutedparathn wax sulionic acids Ghloro-substituted parafin wax sulfonicacldsUnsaturated sulfonic acids derived from polyalkylcnos contaming at least15 carbon atoms, e. g.: A

Tetraisobutylcne sulionlc acids Tetra-amylene sullonic acidsCycloaliphatic sulionic acids, e. g;

Petroleum naph henc sulfonlc acids Cetyl-eyclopentyl sulfonic acidsLauryl-cyclohexyl sulfonic acids Bls-(diisobutyl) cyclohexyl sullomcacids Monoand poly-wax substituted cyclohexyl sullonic acids Additionalexamples of sulphonic acids and/or salts thereof which can be employedas starting materials are disclosed in the following U. S. patents:2,174,110; 2,174,506; 2,174,508; 2,193,824; 2,197,800; 2,202,791;2,212,786; 2,213,360; 2,228,598; 2,233,676; 2,239,974;2,263,312;'2,276,090; 2,276,097; 2,315,514; 2,319,121; 2,321,022;2,333,568; 2,333,788; 2,335,259; 2,337,552; 2,346,568; 2,366,027;2,374,193; and 2,383,319.

However, preferably, is intended to use as starting materials, theproducts derived in accordance with the processes of the aboveenumerated patents on the following initial materials:

Lubricating oil fractions Petrolatnm Paraflin wax Petroleum naphthenesWhite oil Gas oil Abietane The higher alkylatedcyclohexanes, e. 3.:

Getyl'cyclohexane Bls-(diisobutyl) cyclohexanes v The higher alkylatedcyclopentanes, e. g: paraflln wax" sub tituted cyclopentane The higheralkylated decahydro-naphthalenes, e. g.: dl-lauryl decahydronaphthalenes The higher alkylated benzencs, e. g.:

Parafiln wax substituted benzene Monoand poly-(triisobutyl) benzenesMoncand poly-(tetraisobutyl) bentenes The higher alkylated naphthalenes,e. g.: Petrclatum substituted naphthalene Paraflin was: substitutednaphthalene Ter. one polymers, e. g.:

, olymerized turpentine Polymerlzed ruenthenes ,alkylene and alkadienepolymers, e. g.:

Polyethylenes Polypropylenes Polybutenes Polyisoprenes, ,e.g. natural rbber .Polybutadlenes r Polycaprylenes (Jo-polymers, e. g.:

Styrene-butadiene co-polymers Styrene-methyl acrylate co-polymersp-Methyl-alpha-methyl-styrene-vinyl chloride tic-polymers The higheraliphatic hydrocarbons, e. g.:

ctadecane Elcosane Tetracosane Pentacosane Heptacosane Triacontane Forthe purposes of this specification and appended claims, it should beunderstood that petroleum sulphonic acids or salts thereof are intendedto cover those compounds derived from petroleum.

It has been found that metal complexes of considerable utility may beproduced When using as the starting material a mixture of at least twodifiei'ent sulfonic acid compounds.

Highly useful in this respect are mixtures containing (a) at least onepetroleum derived sulfonic acid compound, and (b) at least one alkylaromatic sulfonic acid compound. Particularly preferred are mixtures ofmahogany sulfonic acids or salts with alkyl-benzene sulfonic acids orsalts. The ratio of equivalents of a/b is preferably between 0.1 and 10.

The following examples illustrate a number of specific combinations ofdifferent sulfonic acid compounds which may be used as startingmaterials for the production of our metal complexes. In each instance,the corresponding salts of the sulfonic acids are also contemplated.

chemical equivalents Mixture No. Components {Mahogany sulfonic acidDi-isododecyl benzene sulfonic acid- {White oil sulfonic acid Mahoganysulionic acid Di-isododecyl benzene sulfonic acid.. {White oil sulionicacid Di-isododecyl benzene sulionic acid {Mahogany sulfonic acidWax-substituted phenol sulionic acid. {Mahogany sulfonic acidWax-substituted naphthalene sulionic acid- {Mahogany sulionic acidWax-substitut ed benzene sulfonlc acid {P etrolatum sulionic acid Whiteoil sulfonic acid..- lMahogany sulionic acid.

Petrolatum sulfonic acid Mahogany sult'onic acid. White oil sulfonicacid. {Polybutene sulionic acid. Mahogany sulionic acid. {Wax sulfonicacid Mahogany sulfonic acid {Eicosyl diphenyl ether sulionic acid.Mahogany sulfonic acid {Tri-capryl diphenyl ether sulfonic acid-Mahogany sulfonic acid tBis- (diisobutyD-phenol sulfonic acid White oilsulfonic acid Cetyl-chlorobenzene sulfonic acid.- Mahogany sulionic acid{Di-cetyl naphthalene sulionic acid.

Mahogany sulfonic acid. [Mahogany sulfonic acid.

White oil sulfonic acid.

{White oil disulionic acid.

Di-isooctadecyl benzene suli Petroleum naphthene suhonic acids..Mahogany sul ionic acid Polybutene-substituted benzene suhonic aci 2O{Di-keryl benzene sulfonic acid. Mahogany sulfonic acid- {Fuel oilsubstituted benzene sulfoni c1 Mahogany sulionic acid {Stearylnaphthalene sulionic acid.

White oil sulfonic acid t, {Wax-substituted phenothioxine sulionic acid.a Mahogany sulionic acid Organic acids in which:

(n) Sulfur is the acid-forming element, for example:

Organic acids containing the SO3H radical, c. g;

Sulfonic acids (prior lists give specific examples) Sulfamic acids, e.g.:

Di-lauryl sulfainic acid Di- 3,9'diethyl-tridecyI-6) suiiamicacidDicetyl-phenyl) suliamic acids Din-cctylcyclohexyl) suliamic acidsThicsuliouic acids, e. g.:

Eicosane thiosulionic acids Paraflin wax thicsulronic acids Parafiin waxsubstituted benzene sulionic acids Oetyl-cyclohexane thiosulfonie acidsOrganic acids containing the S 0 H radical, c. g.:

ulflnic acids, e. g.:

n-Octadecanc sulflnic acids Paraflin wax suliinic acids Petroleumsulfinic acids Paratiin wax substituted naphthalene sulfinic acidsPetroleum naphthene sulfinic acids Di-capryl-cyclohexane sulfinic acidsThionamic acids, e. g.:

Myricyl thionarnie acid Di-cctyl thionamic acid Di-(lauryl-phenyl) thioramic acids Earaflin wax substituted cyclohoxyl thionamie acids Partialesters of polybasic inorganic sulfur acids, e. g.

Mono-esters of sulfuric acid, e. g.

Mono-docosyl sulfate Mono-(dlisobutyl-phenyl) sulfatesMono-(cetyl-cyclohexyl) sulfates Mono-esters of suliurous acid, e. g.:

Mono-octadecyl sufites Mono-(eicosyl-phenyl) sulfitesMono-(hydroabietyl) sulfites Miono-estel's oi thiosulfuric acid, e. g.:

Mono-pentacosyl thiosulfate Mono-Edi-capryl naphtheyl) thiosull'atesMonomyristyl-cyclopentyl) thiosulfates (b) Selenium IS the acid-formingelement, for example:

Selcnonic acids, e. g.:

Paraflin wax selenonic acids Di-lauryl-benzene sclenonic acidsGetylyclohexane selen onic acids Scleninlc acids, e. 11.:

Heneicosane seleninic acids '1rr-capryl-nephthalone seleninic acidslaratfiu wax substituted cyclohexane seleninic acids Partial esters oipolybasic inorganic selenium acids, e. g.:

Mono-esters 0t selenic acid, e. g.:

Mono-tricosyl selenate Mono-(n onadecyl-phenyl) seleuatcsMono-(di-n-octyl-cyclohexyl) selenatos Mono-esters oiselenious acid, e.g.:

Mono-myricyl sclenite Mono-(eicosyl-naphthyl) selenitesMono-(cetyl-cyclopentyl) selenites (c) Tellurium IS the acid-formingelement, for example:

Telluronic acids, e. g;

Paratiin wax telluronic acids Di-capryl-anthracene telluronic acidsPcntacosyl-cyclohexane telluronic acids Tellurinic acids, e. g.:

Heptacosane tellurinic acids Di-nonyl-benzene tellurinic acidsDi-lauryl-cyclohexyl tellurinic acids Partial esters of polybasicinorganic tellurium acids, e. g.:

Mono-esters of tclluric acid, e. g.: Mono-henelcosyl tellurateMono-(docosyl-phcnyl) tellurates Mono-(tetracosyl-cyclohexyl) telluratesMono-esters of tellurous acid, e. g.:

Mono-octadecyl tellurites Mono-(di-octyl-phenyl) telluritesMono-(cetyl-cyclohcxyl) tellurites (:1) Carbon 15 the acid-formingelement, for example:

Organic acids containing the OOaH radical, e. g.:

Carboxylic acids, e. g.:

Stearlc acid Behenic acid Carnaubic acid Oerotic acid ig mo ec ar wcig taci s from t e oxidation of a wax and other petroleum fractions par finOlcic acid Erucic acid Cetoleic acid Cetyl-benzoio acidsEicosyl-naphthoic acids Paratiin wax substituted hydroxy-benzoic acidsDi-lauryl-enthracene carboxylic acids Petroleum naphthenic acids Abieticacid Hydroabietic acid fletraeosyl-cyclohexane carboxylic acidsN-substituted carbamic acid, a. g.:

Di-octyl-carbamic acids Mono-cetyl carbamic acids Di-(hexyl-phenyl)carbamic acids Mono-(lauryl-phenyl) carbamic acids Di-(amyl-cyclohexyl)carbamic acids Mono-(lauryl-cyclohexyl) carbamic acids Organic acidscontaining the OX:EL radical, where X is oxygen, sulfur, selenium, ortellurium, and at least one X is other than oxygen, e. g.:

Thiocarboxylic acids, e. g.:

Monoand di-thio stearic acids Moncand di-thio oleic acids Monoanddi-thio mellissic acids Moncand d -thio parafiin wax substituted henzoicacid Monoand di-thio eicosyl-naphthoic acids Monoand di-thiooctadecyl-cyclohexane carboxylic acids Monoand di-thio petroleumnaphthenic acids N-substituted thiocarbamic acids, e. g.:

etyl monoand di-thio carbamic acids Di-capryl monoand di-thio carbamicacids Lauryl-phenyl monoand di-thio carbamic acids Di-(octyl-phenyl)monoand dl-thio carbamic acids Npnadecyl-cyclohexyl monoand di-thiocarbamic acids Di-(heptyl-cyclohexyl) monoand di-tbio carbamic acidsSelenocarboxyllo acids, e. g.:

Monoand dl-seleno staeric acids Monoand di-seleno oleic acids Monoanddl-seleno tetracosyl-benzoie acids Monoand di-seleno petroleumnaphthenic acids Tellurocarboxyhc acids, e. g.:

Monoand di-telluro oleic acids Monoand di-telluro cetyl naphthoic acidsMonoand di-telluro hydroabietic acid Partial esters of polybasicinorganic carbon acids, e. g.:

Mono-esters of carbonic acid, c. g.:

Mono-ercosyl carbonate Mono-(cetyl-phenyl) carbonatesMono-(lauryl-cyclohexyl) carbonates Mono-esters ot thiocarbonic acids,e. g.:

Monggdocosyl esters of mono, di-, and tri-thio carbonic ac1Mono-(myristyl-phcnyl) esters of mono, di-, and tri-thio carbonic acidsMono-esters of selenocarbonic acids, e. g.:

Mouo-pentacosyl esters of mono-, di-, and tri-seleno carbonic dsMono-ceryl-phenyl esters oi mono-, di-, and tri-scleno carbonic acidsMono-(lauryl-eyclohexyl) esters i mono-, di-, and trl-seleno carbonicacids Mono-esters of tellurocarbonic acids, e. g.:

Mono-octadecyl esters of mono-, di-, and tri-telluro carbonic a sMono-(parafiin wax substituted phenyl) esters of mono,

di, and tri-telluro carbonic acids Mono-(cetyl-cyclopentyl) esters ofmono-, dr-, and trr-telluro carbonic acids.

It is also intended to employ as starting materials those high molecularweight acids which are prepared from the well-known 0x0 andFischer-Tropsch proc- (e) Nitrogen is the acid-forming element, forexample:

Nltrollc acids, e. g.:

Docosyl mtrolic acid Oetadccyl-naphthyl nitrolie acids Parafiln waxsubstituted cyclohcxyl nitrolic acids Nltrosolic acids, 0. g.:

Hexacosyl nitrosolic acid Nonadecyl-phenyl nitrosolic acidsDl-octyl-cyclohexyl nitrosolic acids Nitronic acids, e. g;

Heneicosane mtronic acids Phenyl-cetane nitronic acidsCyclohexyl-octadecane nltromc acids Nitroic acids e. g.:

Octacosyl nitroic acid Getylhenyl nitroic acids Laury -cyclohexy1nitroicacids Carbazy lic acids, e. g.:

Eicosane carbazylic acid Cetyl-benzene carbazylic acidsLauryl-cyclohexane carbazylrc acids Also useful as starting materialsfor the production of metal complexes are the pentavalent organic acidsof phosphorus which contain at least one carbon te-phosphorus bond; i.e., those acids of the general formula:

wherein X and X are oxygen or sulfur, R is an organic radical bonded tophosphorus through a carbon atom, is is 1 or 2, and R11. contains atotal of at least 12 carbon atoms.

When n is 2, there are of course two organic radicals present. Suchradicals may be the same or dilferent; for example, R2 may represent twooctyl radicals or a decyl radical and a hexyl radical.

Qther useful carbon-to-phosphorus bonded pentavalent organic acids ofphosphorus, but whose exact structures have not yet been ascertained,are those acids prepared from aliphatic, cycloaliphatic and/or aromaticcompounds which are devoid of hydroxyl, sulfhydryl, and keto groups bytreating such compounds with at least one sulfurizing and phosphorizingreagent such as PSCls, P285, P437, P483, P485, P285 plus sulfur, PClaplus sulfur, elemental phosphorus plus sulfur, and the like, andoptionally further treating with a hydrolyzing agent such .as water,steam, and/or metallic base. The preporation of such materials isdisclosed in U. S. Patents Nos. 2,316,085; 2,316,086; 2,316,087;2,316,088; 2,316,- 089; 2,316,091; 2,316,078; 2,316,079;,2,316,080;2,316,- 081; 2,316,082; 2,316,083; 2,316,084; and 2,367,468.

Typical organic starting materials for the production of these-acids aregiven hereinbelow:

Lubricating oil fractions, especially those 01 high aromaticityPetrolatum Paraflln wax Paraflin oil Petroleum naphthcnes White oil Gasoil Abietane Oycloali hatie hydrocarbons and their alkylatcdderivatives, e. g.:

Oyc ohexane Methyl-eyclohexane Di-methyl-cyclohexanes Ethyl-cyclohexancButyl-cyclohexanes Hexyl-cyclohexanes DecahydronaphthalencCetyl-cylcohexane B1s-(diisobutyl) cyclohexanes The alkylatedcyclopentaues, e. g.:

Ethyl-cyclopentane Pararfin wax substituted 'cyclopentane The alkylateddecahydro-napthalenes, e. g.:

Di-ethyl decahydronaphthalene Di-lauryl decahydronaphthalenes Aliphatichydrocarbons, e. g.:

Hexanes Heptanes Octanes, e. g.:

n-Octane Diisobutane Deeanes Dodeeanes Mixtures of the lower aliphatichydrocarbons such as those found in e. a: Gasoline Kerosene NaphthaOctcdecane Eicosane 'letracosane Pentacosane Heptacosane TriacontnneAromatic hydrocarbons and their alkylated derivatives, c. g.:

Benzene Toluene Xylenes Ethyl-benzene Amyl-benzenes Octyl-benzenesNaphthalene Methyl-naphthalenes Ethyl-naphtbalencs Butyl-naphthalencsAnthracene Methyl-anthracenes Diphenyl Terphenyl The Higher alkylatedbenzcnes, e. g.: Paraffin wax substituted benzene Monoandpoly-(triisobutyl) benzenes Monoand poly-(tetraisobutyl) benzencs Thehigher alkylated naphthalenes, e. g.:

Petroleum substituted naphthalene Paraflin wax substituted naphthaleneTerpene polymers, e. g.:

Polymerized turpentine Polymerized menthenes Alkylene and alkadienepolymers, e. g.:

Polyethylenes Polypropylenes Polybutenes Polyisoprenes, e. g. naturalrubber Polybutadienes Polyeaprylenes Go-polyrners, e. g.:

Styrene-butadiene co'polymers Styrene-methyl acrylate err-polymersp-Methyl-alpha-methyl-styrene-vmyl chloride (ac-polymers Acids ofphosphorus having at least one carbon-tophosphorus bond, when used inadmixture with at least one oil-soluble sulfonic acid compound, havebeen found to provide highly useful starting materials for producing ourmetal complexes. Particularly valuable metal complexes for, some uses,as for example in lubricants, are obtained when using as a startingmaterial a combination of petroleum sulfonate and thecarbon-to-phosphorus bonded acid obtained by treating polyhutylenes inthe molecular Weight range of 300 to 5000 with a mixture of P255 andsulfur.

(1') Phosphorus is the acid-forming element, for example:

Phosphinic acids; RxP(OH)3 wheres is 1 or 2, c. g.:

Pentacosyl phosphinic acid Di-lauryl phosphinic acid Cetyl-phenylphosphinic acids Di-(octyl-phenyl) phosphinic acids Octadecylcyclohexylphosphinic acids Di-(nonyl-eyclohexyl) phosphinic acids Phosphonicacids; RxP(0H)a-= where a: is 1 or 2, e. g.:

Octadecyl phosphonic acid Di-lauryl phosphonlc acid Ceryl-naphthylphospbonic acid Dl-(capryl-naphthyl) phosphonic acid Oet(yl-cyclohexylphosphonic acid 131- decyl-cyclohexyl) phosphonlc acid Thiophosphinicacids; RxP(ZH)a-, where: is l or 2 and Z is either or S with at leastone Z being sulfur, e. g.: Monoand di-thio cetyl phosphinic acidDi-lauryl thiophosphinic acid Monoand di-thio eicosyl-phenyl phosphinicacids Di-capryl-phenyl thiophosphim'c acid Monoand di-thiooctadecyl-cyclohexyl phosphinic acids Di-(nonyl-cyclohexyl)thiophosphinic acids Thiophosphonic acids; RxPZ(ZH)a-=, where x is 1 or2 and Z is either 0 or S with at least one Z being sulfur, e. g.:

Mono-, di-, and tri-thio octadecyl phosphonic acids Di-decylthiolphosphonic acids Di-deeyl thionophosphonic acids Mono-, di-, andtri-thio docosyl-phenyl phosphonic acids Di-(amyl-phenyl)dithiophosphonic acid Mono-, di-, and tri-thio cetyl-cyclohexylphosphonic acids Di-(nonyl-cyclohexyl) dithiophosphonic acid Partialesters of polybasic inorganic phosphorus acids, e. g.:

Mono-esters of phosphorous acid, e. g.:

Mono-cicosyl phosphite Mono-(lauryl-phenyl) phosphitesMono-(cetyl-cyelohexyl) phosphites Mono-esters of thiophosphorous acids,e. g.:

Mono-S-docosyl thiophosphite Mono-O-docosyl dithiophosphiteMono-(O-cetyl-phenyl) clithiophosphites Mono-(octyl-cyclohexyl)trithiophosphites Monoand di-esters of phosphoric acid, e. g;

Monoand di-lauryl phosphates Monoand di-(dodecyl-phenyl) phosphatesMonoand di-(nonyl-cyclohexyl) phosphates Monoand di-esters ofthiophosphoric acids, e. g.:

0,0-di-n-hcxyl thiolthionophosphate 0,0-di-n-hexyl thionophosphate0,0-di-(s-methyl-sec-arnyl) thiolthionophosphatc O,S-di-n-heptyldithiolthionophosphate 0,0-di-(2-ethyl-hexyl) thiolthionophosphate0,0-di-capryl thiolthionophosphate 0,0-di-(2,4,4-trimethyl-amyl)thiolthionophosphate O,S-d.i-n-nonyl dithiolphosphate0,0-di(3,5,5-trimethyl-hexyl) thiolthionophosphate 0,0-di-n-decylthiolthionophosphate S,S-di-n-undecyl dithiolphosphate 0,0-di-laurylthiolthionophosphatc S-cetyl dithiolphosphate 0,0-di-cctylthiolthionophosphate 'ihiolthionophosphates of the general formula(CnHIn'H' 0)zPSSH, where n is a number of from 20 to 50, e. g.:O-odi-(paraiiin wax) thilthionophosphates 0,0-di-myricylthiolthionophosphate 0,0-di-carnaubyl thiolthionophosphate0,0-di-(tert-amyl-phenyl) thiolthionophosphates0,0-bis-(diisobutyl-phenyl) thiolthionophosphate 0,0-di-(decyl-phenyl)thionophosphates O-cetyl-phcnyl-O-napthyi thiolthionophosphates0,0-di-(methyl-cyclohexyl) thiolthionophosphates0,0-di-(amyl-cyclohexyl) thiolthionophosphates Pentacosyl-cyclohexyitetrathiophosphates O,S-di-(heptyl-cyclohexyl) dithiolthionophosphatesPartial esters of pyrophosphoric acid Mono-, di-, and tri-eicosylpyrophosphates Mon0-, di-, and tri-(ceryl-phenyl) pyrophosphate Mono-,di-, and tri-(cetyl-cyclohexyl) pyrophosphates Partial esters ofpyrophosphorus acid Mono-, di-, and tri-octadecyl pyrophosphites Mono-,di-, and tri-(myricyl-phenyl) pyrophosphites Monc-, di-, andtri-(cetyl-cyclopentyl) pyrophosphites Partial esters of polyphosphoricacids, e. g.:

Mono-, di-, tri-, and tetra-ceryl triphosphates Molilio, di-, tri-,tetra-, and penta-(dilaurylphenyl) tetraphosp a es Mono-, di-, tri',tetra-, and penta-, and hexa-(docosyl-cyclohexyl) pentaphosphatesPartial esters of polyphosphorous acids, e. g.:

Mono, di-, tri-, and tetra-ceryl triphosphites Mono-, di-, tri-, tetra-,and penta-(stearylphenyl) tetraphosphites Mono-, di-, tri-, tetra-,penta-, and hexa-(paraflin wax substituted cyclohexyl) pentaphosphitesPartial esters of pyrothiophosphoric acids, e. g.:

Mono-, di-, and tri-eicosyl pyrodithionophosphates Mono-, di-, andtri-(cetyl-naphthyl) pyrcheptathiophospbates Mono-, di-, andtri-(hydroabietyl) pyrothionophosphates Partial esters oipyrothiophosphorus acids, e. g.:

Mono-, di-, and tri-ceryl S-pyro thiophosphites Mono-, di-, andtri-(docosyl-phenyl) O-pyrotetrathiolphosphites Mono-, di-, andtri-(lauryl-cyclohexyl) pyropentathiophosphites Partial esters ofthiopolyphosphoric acids, e. g.:

Mono-, di-, tri-, and tetra-ceryl decathiotriphosphates Mono-, di-,tri-, tetra-, and penta-(di-caprylphenyl) tetrathionotetraphosphatesMono-, di-, tri-, tetra-, penta-, end hexahydroabietylpentathionopentaphosphates Partial esters of thiopolyphosphorous acids,e. g.:

Mono-, di-, tri-, and tetra-myricyl heptathiotrlphosphites Moire tri-,tetra-, and penta-(laurylphenyl) trithiotetrap osp es LIOI1O3 di-, tri-,tetra-, penta-, and hexa- (petroleum naphthenyl)tetrathiopentaphosphites Arsenic is the acid-forming element, forexample: Arsinic acids, e. g.:

Mono-cetyl arsinic acid Di-(lauryl-phenyl) arsinie acidsMono-hydroabietyl arsinie acid Arsonic acids, e. g.:

Mono-ceryl arsenic acid Di-(octyl-naphthyl) arsonic acidsMono-(myricyl-cyclohexyl) arsenic acids Partial esters of polybasic,inorganic, arsenic-derived acids, e. g.:

Mono-esters oi arsemous acids, e. g.:

Mono-ceryl arsenite Mono-(stearyl-naphthyl) arsenltes Mono-(petroleumnaphthenyl) arsenites Monoand di-esters oi arsenic acid, e.g.:

Monoand di-eicosyl arsenates Monoand dl-(lauryl-naphthyl) arsenatesMonoand di-(cetyl-cyclopeutyl) arsenates (h) Antimony is the acidforming element, for example? Stibonic acids, e.g.:

Di-lauryl stibonic acid Di-(ceryl-phenyl) stibonic acidsDi-(octyl=cyclohexyl) stibonic acids J Partial esters of polybasicinorganic antimony acids, e.g.:

Mono-esters of antimonous acid, e.g.:

Mono-ce'ryl antimonite Mono-(eicosyl-phenyl) antimonitesMono-(lauryl-cyclohexyl) antimonites Monoand dl-esters of antimonicacid, e.g.: Monoand di-cetyl antimonic acids Monoanddi-(tetradecyl-naphthyl) antimonic acids (2') Silicon is theacid-forming element, for example:

Siliconic acids; R-SiOOH, e.g.:

Oeryl siliconic acid Myristyl-phenyl siliconic acids Hydroabietylsiliconic acid Partial esters of silicic acids, e.g.:

Mono-myricyl metasilicate .Di-(lauryl-naphthyl) orthosilicateMono-(petroleum-naphthenyl) orthosllicatc (j) 'iin is the acid-formingelement, for example:

Staunonic acids; R-SnOOH, e. g;

Eicosyl stannonic acid Cetyl-phenyl stannonic acids Di-capryl-cyclohexylatannonic acids (1:) Lead is the acid-forming element, for example:

Plumbonic acids; R-PbOOH, e. g.:

Ceryl plumbonic acid Di-lauryl-phenyl piumbonic acid Hydroabietylplumbonic acid While the above compounds and classes thereof are usefulfor the purposes of this mvention, 1t should be: understood that theyare not all equivalent, but that under certain conditions some are moredesirable or effective than others.

THE PROMOTER The materials useful in the present process as so-calledpromoters have a function which is somewhat diiierent from the functionof the materials referred to as pro meters in our co-pcnding parentapplications. In certain of the processes contemplated in said parentapplications, the promoter material has a function of assisting, to acertain extent at least, in bringing at least some of the so-calledbasing material into the complex. In the present case the promoter doesnot have that function in that no free basing material is present in thereaction mass. In the present case, therefore, the so-called promotermaterial serves first as the source for the metal present in the complexwhich is in excess of that present as the metal of the normal salt ofthe starting acid. The anion of the promoter liberated from the promotermaterial by the subsequent acid treatment may, of course, have an efiectupon the nature of the ultimate complex formed between the normal saltof the starting acid and a compound formed from the metal derived fromthe promoter, and it is possible that this last-named effect may besimilar to the eifcct of the promoter in those processes of our parentapplications wherein the promoter material is employed in conjunctionwith added inorganic basing material.

The promoter materials which have been found most useful in the presentprocesses are compounds of the phenols and enols. The phenolic andenolic organic compounds are such that the anions thereof may be readilyliberated from the metal compounds thereof by a simple acid treatingprocess, as utilizing, for example, CO2 and S02, as well as HzS and CS2.While promoter materials formed from acid-reacting compounds havingionlzations constants higher than phenols and enols might be usefulunder certain circumstances, they would require the use of such astrongly acidic material in the subsequent acid treating step that greatcare would need to be exercised during such step to prevent unfavorableeffects on the metal complex which is desired as the end product.Therefore, in the present case, we are concerned only with the use aspromoter materials of phenolic and enolic compounds, since by the use ofthese together with the type of acid treating materials mentioned above,it is possible to very easily .and economically produce complexes whichhave great utility. The phenolic compounds acids Naphithol sulfinieacids, e. g.: beta-naphthol al ha-sulfinic c Phenols andalkylated-pherols having a sulfur-bearing substituent group other thanSO;H or -S0,H, for example:

Phenol sulfides, e. g.: di-(p-hydroxy-phenyl) sulfide Naphthol sulfides,e. g.:

Alpha-naghthol sulfides Beta-nap thol sulfides Anthrol sulfidesPoly-hydroxy-aryl sulfides, e. g.:

Hydroquinone sulfide Oatechol sulfides Resoreinol sulfides Pyrogallolsulfides Phloroglucinol sulfide Naghthoresorcinol sulfidesDiydroxy-anthracene sulfides, e. g.:

Rufol sulfides Ohrysazol sulfides Propyl-phenol sulfides, e. g.:p-iso-propyl-phenol sulfides Butyl-phenol sulfides, e. g.:

p-t-Butyl-phenol sulfides o-sec-butyl-phenol sulfides Ethyl-naphtholsulfides, e. g.:

Ethyl alpha-naphthol sulfides Di-ethyl-beta-naphthol sulfidesAmyl-resorcinol sulfides Methyl-cyclohexyl-eatechol sulfides Phenoldisulfides, e. g.: di-(p-hydroxy-phenyl) disulfide N aphthol disulfidesAnthrol disulfides Poly-hydroxy-aryl disulfides, e. g.:

Hydroquinone disulfide Resorcinol disulfides Na hthoresorcinoldisulfides Diydroxy-anthracene disulfides, e. g.:

Rulol disulfides Ohrysazol disulfides Cresol disulfides, e. g.: p-Oresoldisulfides o-Cresol disulfides Butyl-phenol disulfides, e. g.:p-t-butyl-phenol disulfid es Amyl-naphthol disulfides, e. g.:t-amyl-alpha-naphthol disulfides Hexyl-cateehol disulfidesrropyl-naphthohydroquinoue disulfides Amyl-dihydroxy-phenanthrenedisulfides Phenol sulfoxides, e. g.: di-(-hydroxy-phenyl) sulioxideNaphthol sulfoxides Anthrol sulfoxides Resoreinol sulfoxidesNaphthoresorcin ol sulfoxides Ethyl-phenol sulloxides, e. g.:-Ethyl-phenol sulfoxides i-ethyl-phenol sulfoxides Butyl-phenolsulfoxides, e. g.: p-t-butyl-phenol sulfoxides Oetyl-eateoholsulfoxides, e. g.:

Oapryl-eateohol sulloxides Diisobutyl-catechol sulfoxides Amyl-naphthclsulloxides Methyl-cyclohexyl-naphthohydroqui:one suh'oxides Phenolsullones, e. g.: di-(p-hydroxy-phenyl) sulfonc Naphthol sultonesPhloroglucinol sulfones Naphthohydroqumone suliones Rulol sulfonesButyl-phenol suliones, e. g.: p-t-butyl-phenol sulfones Propyl-naphtholsuhones, e. g.: iso-propyl-beta-naphthol sullones Hexyl-catecholsulfones Ethyl-uaphthohydroquinone sulfones Sulfur analogs of phenoliccompounds, for example:

hi0 enol p-Et yl-thiophenol so-propyl-thiophenol p-t-Butyl-thiophenclp-t-Amyl-thiophencl bec-hexyl-thiophenols Oyelo-hexyl-throphenolsn-Heptyl-thiophencls Diisobutyl-thiophenols3,5.5-trimethyl-n-hexyl-thiophenol n-Decyhphenols Hexadecyl-thiophenolso-Chloro-thiophenol p-Nitro-thiophenol p-Amino-thiophenol Thiosalicylicacid t-Mercapto-l-naphthoic acid From the examples of phenohc compoundsgiven above, it will be observed that throughout the specification andits claims when use 1s made of the term a phenol, we intend to includeall those orgamc compounds which contain in their molecule a benzenering containing at least one hydroxyl or sulphydroxyl group irrespectiveof what other substituents may be contained in the molecule. Thus, thisterm is 1nclus1ve not only of the oxy-phenols but the thio-phenols aswell as the substituted derivatives thereof. Llkewise, throughout thespecification and in the dams where use is made of the term a phenoliccompound we intend to include not only compounds WhlCh can be referredto as a phenol as above defined,

14 but also all derivatives thereof including the metal salts. It shouldbe noted also that from the examples given above, the term a phenol isinclusive of those compounds in which the 6-membered ring to which thecharacterizing hydroxyl group is attached may have one or more otherring structures connected thereto or fused therewith.

THE ENOLIC COMPOUNDS The term enolic organic compounds as used in thespecification and appended claims refers to tautomeric organic compoundsof the established type, for example, as illustrated in Advanced OrganicChemistry, by G. W. Wheland, John Wiley & Sons, New York, 1949, chap.14, pp. 580 to 646.

Generally, the enolic organic compounds include a variety of classes ofcompounds such as aliphatic nitro compounds (i. e. aci-nitro compounds),oximes, imines, imides, amides, keto-esters, polyesters, andpolyketones. It will be noted that the term enolic carbonyl includesketo-esters, polyesters, and polyketones.

The aliphatic nitro compounds (aci-nitro compounds) useful as promotersinclude, for example, l-(para-nitrophenyl)-2-nitrobutane; gamma-nitromethyl hexoate, lchloro l-nitropropane, l-nitropropane, etc.

The oximes useful as promoters include, for example, benzalacetoneoxime, quinone mono-oxime, isophorone oxime, etc.

The amides useful as promoters include, for example,

-ethyl benzamide, ortho-chlorobenzamide, benzamide, acetanilide,thiodiglycolic acid diamide, acatamide, etc.

The enolic carbonyl compounds useful as promoters include, for example:keto-esters, such as, phenyl acetoacetate, ethyl acetoacetate, benzylacetoacetate, chloronaphthol acetoacetate, etc.; polyesters, such as,dibenzyl malonate, diethyl malonate, triethylcarballyate, etc.; andpolyketones, such as, benzoyl acetone, acetyl acetone, etc.

THE ACIDIC MATERIAL As previously indicated, one form of the process ofthe present invention includes the step of treating the immediateproduct with an acidic material for the purpose of liberating therefromat least a portion of the material previously referred to as thepromoter. A particularly elfective acidic material which has beenutilized for this purpose is carbon dioxide. We are aware of the factthat Mertes in his above-identified Patent No. 2,501,731 suggestedtransforming a sodium hydroxide-caleium sulphonate complex into thesodium carbonate-calcium sulphonate complex or the correspondingbicarbonate complex by blowing the hydroxide complex with carbon dioxideat elevated temperatures.

In our process, the step of treating with an acidic material such ascarbon dioxide or even with air has the effect of liberating from theimmediate product formed a part at least of the anionic radical of thecompound used as the promoter material. Thus the presence in theimmediate product of the promoter material, in combined form, clearlydistinguishes the immediate product from any'organic salt complex typematerial heretofore produced. Moreover, the nature of the product formedby regenerating from the immediate product at least a portion of theanionic radical of the promoter material leaves that product with acomposition which is quite different from prior art organic complexes.It is recognized that in accordance with the present invention, the saltform of promoter can be employed in forming the salt complex. However,notwithstanding this fact, upon treating the salt complex with theacidic material to be more particularly defined below, this saltcompound is released or liberated from association in the salt complexas the ionizable compound and not the salt.

The acidic material employed for this purpose can be either a liquid,gas, or solid just so long as the material when present in the masscontaining the salt complex will possess an ionization constant greaterthan the promoter which is released or liberated from association in thesalt complex. Thus, for the purpose of this specification and theappended claims, it is to be understood that the acidic materialincludes a liquid, gas, or solid prior to being incorporated in the masswhich contains the salt complex.

In the present invention, the acidic material usually employed is anacid or a gas. The acids can include the strong or weak types, such as,for example, hydrochloric, sulphuric, nitric, carbonic, acetic acids,etc., Whereas the gas is for the most part an anhydride or an acid or anacid anhydride gas.

The large number and variety of acidic materials can be best illustratedby the following specific examples, viz. HCl, S02, S03, CO2, air, N02,H28, N203, PCls, SOClz, C102, HzSe, BFs, CS2, COS, etc.

From the above examples of compounds and classes of compounds which canbe used as acidic materials, it should be understood that all of themare not equivalent for this invention because under certain conditionssome are more desirable or etfective than others.

Generally, the complex formed is prepared by heating the components, ata superatmospheric temperature while insuring thorough mixing and thenfurther heating said mixture to substantially remove all free water oralcohol, including water and alcohol of hydration which may be present.The following methods illustrate the manner by which the complex can beformed, namely:

(a) The compound AH or the salt thereof, is added to the oil-solublesalt of an acidic organic compound, followed by addition of an aqueoussolution or suspension the salt or base thereto. The mixture is held ata superatmospheric temperature for a reasonable length of time whileinsuring thorough mixing, and then the total mixture is further heatedto substantially remove all free water or alcohol including water oralcohol of hydration which may be present.

(1')) The salt or base in a dry state is added to a mixture ofoil-soluble acidic organic compound or salt thereof, the compound AH orthe salt thereof and either water, alcohol, or mixtures of alcohols orwater and alcohol; heated to a superatmospheric temperature whileinsuring thorough mixing and then further heated to remove substantiallyall free water or alcohol including water or alcohol of hydration whichmay be present;

(c) The acidic organic compound is mixed with the compound AH or thesalt thereof, when an aqueous solution or suspension or an alcoholicsolution or suspension of the salt or base is added thereto. The mixtureis heated and agitated at a superatmospheric temperature for a timesulficient to insure thorough mixing and followed by subjecting thetotal mixture to dehydration conditions in order to remove substantiallyall free water or alcohol including water or alcohol of hydration whichmay be present.

(d) A mixture of the oil-soluble acidic organic compound or the saltthereof, the compound AH or the salt thereof, and the salt or base isheated and agitated at a superatmospheric temperature for a timesuficient to insure thorough mixing, and followed by heating the totalmixture in order to remove substantially all free water or water ofhydration which may be present.

(:2) The sediment when formed from any of the aforementioned methods canbe employed either alone or with an additional amount of compound AH orthe salt thereof in any of the three methods given above.

(f) In any of the methods discussed herein for preparing a salt complex,a substantial increase in cationic salt-forming radical content isefiected by treating the mass with an acidic material just aftersubstantial amounts of water or alcohol or both, are driven off and justbefore the mass is filtered.

In all of the methods described above for preparing the salt complex,the step of removing substantially all free water or alcohol includingwater or alcohol of hydration which may be present is accomplished at atemperature not substantially in excess of 350 0, preferably about to200 C. The technique employed to remove the alcohol or water includes,for example, a conventional flash operation, heating undersubatmospheric, atmospheric, or superatmospheric pressures. It can,therefore, be seen that the temperature as well as the time foreifecting the substantial removal of the alcohol of water will generallyvary considerably depending on the technique employed therefor.Generally, the time required to effect substantial removal of water oralcohol when employing drying other than flash techniques is about 15minutes or less, and can be as high as 10-15 hours. Usually, however,atmospheric pressures will be employed for such an operation, andconsequently it will usually require about 1 to 5 hours to removesubstantially all water or alcohol which may be present. At a laterstage of the process, the acidic material when used in gaseous form maybe used to remove the last portion of water.

For the purposes of this specification and the appended claims, therelative amounts of (1) the oil-soluble acidic organic compounds orsalts thereof, and (2) the promoter is expressed as the ratio ofequivalents" of the former (l) to the latter (2). In accordancetherewith, the ratio of equivalents is from about 1 to 10 to about 10 to1, preferably from about 3 to 2 to about 7 to 2. The amount of salt orbase employed in the process will be sufiicient to have present in thetotal mass at least more than about one equivalent of cationicsalt-forming radicals including those present in the oil-soluble acidicorganic compound or the salt thereof and the promoter per equivalent ofoil-soluble acidic organic compound or salt thereof plus the promoter.

The treatment of the salt complex with an acidic material is employedwhen it is desirable to lower the basic number of the salt complex and/or partially or substantially recover the promoter. This treatment isefiected at a temperature of about 25 to 250 C., preferably about to C.,and by employing about 0.5 to 20% of acidic material based on the weightof salt complex. The time of treatment with the acidic material can varyconsiderably depending on the desired result. As would be expected,short periods of treatment might cause only partial liberation orrelease of the promoter or relatively small decreases in the basicnumber of the salt complex; however, in general, periods of treatmentwill range from about 0.25 to 30 hours. In most cases, and particularlywhere it is desired to recover the promotor, the amount of acidicmaterial used should be at least equivalent to the amount of cationicsalt forming radicals present as the salt of the ionizable form ofpromoter. When it is desired to produce a product having substantiallyneutral reaction, the amount of acidic material used should be at leastequivalent to the total cationic salt forming radicals in excess of thatpresent as the normal salt of the oil soluble organic acid.

In those instances where salts or bases containing metal are employed asthe basing agent the metal content of the complex will be defined as theratio of the total metal in the salt complex to the amount of metalwhich is in the form of a normal salt of the oil-soluble acidic organiccompound. In accordance therewith the present invention includes saltcomplexes containing metal ratios greater than 1, and up to about 10 ormore. As for those complexes which are treated with an acidic material,it is to be noted that the metal ratio is substantially the same as inthe complex prior to treating. Consequently, for acidic material treatedcomplexes, the same metal ratios will apply as given above. Likewise,when the salt complex is treated with an acidic material and thepromoter is removed from the resultant product by distillation orotherwise, it is found that the metal ratio will be substantially thesame as in the salt complex before treating with the acidic material.

Since the present invention includes complexes which do not containmetal in combination therewith, it'is con venient, therefore, as a meansof designating the amount of overbasing to employ the ratio of totalcationic saltforming radicals in the salt complex to the amount ofcationic salt-forming radicals which are in the form of a normal salt ofthe oil-soluble acidic organic compound. Hereinafter, this ratio will bereferred to as the cationic salt-forming radical ratio. In accordancetherewith, the cationic salt-forming radical ratio of the salt complexwill be in the same range as given hereinabove for the metal ratio.

It has been found that the salt complex can be prepared by using smallquantities of water, alcohol, or mixtures of both, such as about 1 moleof same per mole of salt or base which is employed as the basing agent.However, more usually about 5 to 50 moles of water, alcohol or mixturesof both per mole of salt or base used, and preferably about 15 to 30moles per mole.

To substantially increase the metal content of the salt complex, thetotal mass is treated withan acidic material just prior to filteringsame to separate the desired salt complex. This treatment is effected ata temperature of about 25 to 250 C., preferably about 120 to 170 C.,using about 0.5 to 20% of acidic material, based on the total mass, andfor a period of about 0.25 to 30 hours. Treatment with an acid anhydridegas may be accelerated by superatmospheric pressure.

In order to better understand the present invention, the followingspecific examples thereof are given; however it should be understoodthat no undue limitations or restrictions should be imposed by reasonthereof.

The following examples give the preparation of a plurality of productswhich range in cationic salt forming radical content from about that ofthe normal salt up to many times that amount.

We have found that sulphate ash and/ or metal content values, and themetal ratio values calculated therefrom, are one of the most reliablemeans for characterizing certain of the salt complexes. As thedescription of the invention proceeds, it will become apparent that theneutralization number of a salt complex is in certain instances anunreliable index of the amount of excess cationic salt forming radicalsin such complex, since it is greatly affected by the type of basingagent employed and can be varied within wide limits withoutsignificantly changing the cationic salt forming radical content of theproduct by treatment of the mass with air, CO2, or the like.

The above is not to be construed as a statement that the neutralizationnumber is not an important property of a salt complex. For some uses,for example in lubricants, it is advantageous in certain instances toemploy a salt complex of a substantially neutral character, whereas inother instances a salt complex of high alkalinity has been found toproduce the desired results.

Example 1 3408 grams of polymerized isobutylene having an averagemolecular weight of about 750 were heated to 210 C. and an intimatemixture of 672 grams of Pass and 84 grams of sulfur flowers was addedthereto over a period of 1.75 hours. After all of the PzS5% mixture hadbeen added, the whole was heated for 1.5 hours at 210 C., diluted with2600 grams of low viscosity mineral oil, and blown with steam for 5hours at 210215 C. The filtered material, a high molecular weightorganophosphorus acid of undetermined structure, had an acid no. of 68and contained 0.9% sulfur and 2.14% phosphorus.

820 grams (1.0 equivalent) of this organo-phosphorus acid, 56 grams (1.5equivalents) of Ca(OH)2, and 200 ml. of water were refluxed for 2 hoursand then elevated to 150 C. to remove substantially all of the water (2hours at 150 C. required). The filtered process mass comprises an oilsolution of the calcium salt of the organophosphorus acid. 1

In a separate vessel, 488 ml. of water, 458 grams (4.88 equivalents) ofphenol, and grams (2.44 equivalents) of Ca(OH)2 were refluxed for 2hours to prepare calcium phenate in situ and in the presence of anexcess of phenol. To this vessel were added 333 grams (0.5 equivalent)of the above-described calcium salt of organo-phosphorus acid and 525grams (0.5 equivalent) of a 45% oil solu tion of calcium petroleumsulfonate (6.5% sulfate ash content). The process mass was refluxed for2 hours at -110 C. and then heated to C. where it was blown with CO2 forone hour. The substantially neutral process mass was then heated to 200C. under reduced pressure. Phenol, freed from calcium phenate by thecarbonation step, was recovered to the extent of 91% in the distillate.The residue was diluted with 300 grams of low viscosity mineral oil andfiltered. The filtrate,

the desired end-product, was a brown, oil-soluble liquid having thefollowing analyses:

Percent sulfur 1.16 Percent phosphorus 0.50 Percent calcium 4.18 Percentsulfate ash (calculated) 14.2 Basic no 16.2 Metal ratio 2.57

Example 2 738 grams of the organo-phosphorus acid described in Example1, 902 grams of low viscosity mineral oil, and 800 ml. of water werestirred at 70 C. Then 111 grams (3.0 equivalents) of Ca(OH)2 were addedand the mass was refluxed for 0.5 hour. Thereafter, grams (5.0equivalents) of Ca(OH)2, 1050 grams (1.0 equivalent) of a 45 oilsolution of calcium petroleum sulfonate, and 1315 grams (14.0equivalents) of phenol were added and the process mass was refluxed for3 hours to prepare calcium phenate in situ and in the presence of anexcess of phenol. Substantially all of the water was removed by heatingto 150 C., at which temperature CO2 was blown through the mass for 2hours to render it substantially neutral on titre. A vacuum was thenapplied and the temperature of the mass was raised to 200 C. to removesubstantially all of the original phenol used. The phenol was liberatedfrom the calcium phenate in the process mass by the carbonation step.

After substantially all of the phenol had been removed, the residue wasfiltered. The filtered end product was a brown, oil-soluble liquidhaving the following analyses:

Percent sulfur 1.32 Percent phosphorus 0.47

Percent calcium 4 7 Percent sulfate ash (calculated) 15.2 Basic no 115Metal ratio 3.22

Example 3 The experiment described in Example 2, was repeated using 590grams 1.0 equivalent) of a 65% oil solution of di-isododecyl benzenesulfonic acid in lieu of the 1.0 equivalent of calcium petroleumsulfonate specified therein. The filtered end product in this instancewas a brown,

Example 4 1046 grams (1.0 equivalent) of a 45 oil solution of calciumpetroleum sulfonate of 6.5% sulfate ash content swarm were i'fii5redwith2'28 ;(2.44 'e c' uivalnts) de t renal and h e'ated to TOD "Cf'Wl iileziddirfg 124 assess 2244 equivalents) of calcium me'thoxide to forinalciuin gilinateirr'situ. fifter the fbcessfiass had ben s'tirred-for 2'hours at '100-120 C., 22" grams of H were aclded "andihe 'Whole was'stirred for 'o'ne-houbat 105 C. The temperature was then elevated to 120C.-arid-GOz =Was blownthi'ough the mass asthete'mperatu're wasegai'nele- "rated to 150 C. Thereafter, the -mass '-''was maintained for 1hour at 150' C.,"stripp'ed of phnol libe'rzite'd by -the carbonation-steat- 210" cxane zo "mfiLjI-Ig absolute p'ressure, "and filtered.(Apiirofiirfia fely 90% of the phenol'was' recovered.)

"The filteredend-product was 'abr'own, oiI-sohible l'iquid'haviiig'thefollowifig analysesz ra es: sorta-..

Basic no 923 Metal ratio 3.03

Exdrir'plefi .459' grams (4.88 equivalerit's) 'of phenolflofi grams(2.44 equivalents) of Ca ("OH=)2, imd- 2Z4 grams of" water wererefiuxedfor'l hours to form calcium phenate 'in' situ and inthepresence' of' excess phenol. "1'046i grams (1 .0 equivalent) of" a 45oilsolfitibn "of calcium petroleum sulfonate were -then addedund thewhole w'as heatea-= to 125 C. to-rernove-the bulk of the'water a'hdabout 32 grams of phenol. Thetemperature'was therfelevated to 150 C.and- Coi-was blown tlirouglf themass forlj hours. u P -distillatewas-colleeted "wiiieh Wes found to consist of 18 grams of water and 42grains of phenol. The prdcess'masswas 'thewfieeted to'"200 Cgjijideiiediled Pressure," "removing, as distillateffib'out 375 'fgrfinhs'iofphenol. "Total "phenolrecoveryw'as Anagrams bf 98 of starting-amount. I

The -residue omfiltration yielded" a "brown; oil-soluble liquidhaving-the "following analyses Percent sulfate ash 18.3 Basic 1Metabra'tio "3:07

\ "282- grams-(3.0eduivalritsy bfibheholf'trins 1 .0

iiiiiral" o l -he residueonifiltration, wielded arbmwnmilzselixbleliquid havirrg flmifollowing anaiyses:

'1'046 grains (1J0"equivalezit) of a"45% oil solution-rot calciumetrolenmsfilfonate, 229 "grams (2:4 equivalents) ofphenolj9u5 grams(2;44"equiva1ent's) 'bftaCMOHh, and 244"g'i'ains ofwater' were stirredat 100lO'5'C.f0r 2 hours to form calcium phenate in situ andin'theabsence of an excess'fshenbl. The process'mass'was'heated'slowlyto 126 CQto remove the bulk r-or the water "and some iahenol. "cbz wasthenblo'wn through themass and the temperaturewasraise'd to 156 C; while'CO'blowing was continued. 4 After the whole had been' maintained'lfor 2henrsat 15-0 "C.-wifl1' C02 blowing; it was heated to f2 1 5 C. underreducedfpressure'toremove'substantialiy'all"of "the phenolliberatedbythe carbonation step. "Totarphenol reeever was wm.

"The" residue was filtered 'to yield a. "brown; oil=solnble 'liquidhaving the following analyses:

Percent :sulfate ashs 18.2 Acid -no-; 2.8 Metel ration 3.06

'Per'ceht siilfate ash -s 18:2 "Basic -m r -10.3 Metal satio "4102Example 10 mage-ems (1 .0 equivalerity'bra 35%" oil 'sblution of ceriumrol'eum siilfona'tef' 2'6 l'gramsbf low viscosity'rld'iiOO-mlI-bf"waterwerestirrd-togtherat 'C. 301 rams "(3:94"equivalentsybf 'Bo mid 94 grams (11F equivaleiit} ofbhenbl' wereaddedand' 'thc whole' was reflux'ed for 3 hours. The temperature of theprocess mass was therr elev'a'ted td 1 '5 0""C:- andbwwas blown throughthe reactants until a substantially neutral titre was obtained onthehiass'fabout 2 hours required). The--process-mass-ivas them-elevated'to 200"- C- and a vacuum was-applied. I Substantially all-of the'phenolused was recovered irr the distillate.

The residue on filtration. yielded a brown; :oil soluble liquid havingthe-following analyses *Pefeenfisulfateash 27.6 Basic -no.- 7 '10.].

TatiO- Example 40a -A fdi1ct similar 'tothatdesci'ibed irrExample I'maybe prepared by following the process described'th'erein butoifiittihg'the"-step wherein thep'ro'cess' is heat'ed' to abu e; underreduced"pressure"ro remove henol.

ln' this ifi'stanc the slid-product retains zi"substantial 'erepbrtiow'oe me*pheriorerigixiiny-usd.

21 1 Example b A product similar to that described in Example 10 may beprepared by following the process described therein but omitting thestep wherein the process mass is heated to 200 C. under reduced pressureto remove phenol.

In this instance the end-product retains a substantial proportion of thephenol originally used.

Example 100 A product similar to that described in Example 4 may beprepared using 2.44 equivalents of para-cresol in lieu of the 2.44equivalents of phenol specified therein.

Example 10d A product similar to that described in Example 4 may beprepared by using 2.44 equivalents of diisobutyl-phenol in lieu of the2.44 equivalents of phenol specified therein. Example Me A productsimilar to that described in Example 4 may be prepared by using 2.44equivalents of I-nitro-propane (an enolic compound) in lieu of the 2.44equivalents of phenol specified therein.

Example 10f Example 10g A product similar to that described in Example 9may be prepared by using 1.0 equivalent of a 45% oil solution of mixtureof equal molecular parts of calcium petroleum sulfonate and calciumdi-isododecyl benzene sulfonate in lieu of the 1.0 equivalent of calciumpetroleum sulfonate specified therein.

The salt complexes produced in accordance with the present invention canbe employed in lubricants including oils and greases, and for suchpurposes as in crankcases, transmissions, gears, etc. as well as intorque converter oils. Other suitable uses for such complexes are inasphalt emulsions, insecticidal compositions, fire-proofing andstabilizing agents in plasticizers and plastics, paint driers, rustinhibiting compositions, pesticides, foaming compositions, cutting oils,metal-drawing compositions, flushing oils, textile treatmentcompositions, tanning assistants, metal cleaning compositions,emulsifying agents, antiseptic cleansing compositions, penetratingagents, gum solvent compositions, fat splitting agents, bonding agentfor ceramics and asbestos, asphalt improving agents, flotation agents,improving agents for hydrocarbon fuels such as e. g., gasoline and fueloil, etc.

More particularly, especially adapted for the preparation of lubricants,paint driers and plastics, particularly the halogen bearing plastics. Inthese respects, the salt complex can be employed in the followingconcentrations based upon the weight of the total composition.

LUBRICANT CONTAINING ORGANIC METAL COMPLEXES While the metal complexesof the present invention are useful per se as improving agents forlubricating greases and oils, especially mineral lubricating oilsintended for the complexes of this invention are 3 use in the crankcasesof internal combustion engines, they are most advantageously employed incombination with one or more additional improving agents of the priorart such as, for example, the numerous prior art oxidation inhibitors,detergents, extreme pressure agents, rust inhibitors, and oilinessagents.

In addition to the above-named types of cooperating improving agents,thepresent invention also contemplates the inclusion, in the finishedlubricant, of materials intended to modify the physical characteristicsof the mineral lubricating oil base. Examples of such materials are foaminhibitors, pour point depressants, viscosity index improving agents,and odor improving agents. Since the types of materials useful asphysical property improving agents are well known to those versed in thelubricant art, it is deemed unnecessary to lengthen the specificationunduly by a recitation of the same.

Particularly eifective lubricating oils for the crankcases of internalcombustion engines can be made by in corporating, in suitable minerallubricating oils, thiophosphate salt-esters and/or phosphorus sulfidetreated unsaturated organic materials along with the metal complexes ofthe present invention. From the viewpoint of cost, effectiveness, andcommercial utility, the most desirable thiophosphate salt-esters for useas oxidation and corrosion inhibitors along with materials of thepresent invention in lubricating oils are dithiophosphate salt-esters ofthe general formula R20/ SM wherein R1 and R2 are the same or radicalsand M is one equivalent of a metal selected from Group II of the Tableand most desirably either zinc or barium. In this connection referencemay be made to the dithiophosphate salt-esters disclosed in U. S.Patents 2,261,047; 2,329,436; 2,344,392; 2,344,393; 2,344,394;2,344,395; 2,342,572; 2,347,592; 2,361,746; 2,358,305; 2,364,283;2,364,284; 2,365,938; 2,382,775; 2,386,207; 2,373,811; 2,410,650;2,417,562; and 2,438,876.

Particularly useful in this respect are dithiophosphate salt-esterswherein R1 and R2 of the above formula are different organic radicals,which materials are the subject of pending applications Serial No.250,959, filed October 10, 1951, and Serial No. 251,139, filed October11, 1951, by Fred C. Goldsmith, and which applications have an assigneecommon to the instant application.

Where such salt ester materials, viz. those which contain dissimilarorganic radicals, are used it is necessary only that the average numberof carbon atoms per atom of phosphorus in the salt ester material be 7.6or more. Thus it is not only possible, but entirely feasible to utilizesuch inexpensive alcohols as ethyl, propyl and butyl alcohols in thepreparation of these dithiophosphate salt ester materials. The use ofdithiophosphate salt ester materials in which R1 and R2 of the abovegeneral formula are the same requires the utilization of organicradicals containing a minium of six carbon atoms. Oil-solubilityconsiderations govern the above minimum carbon atom contents.

Phosphorus sulfide treated unsaturated organic materials useful inconjunction with the metal complexes of the present invention include,for example, phosphorus sulfide treated acyclic and cyclic unsaturatedhydrocarbons and phosphorus sulfide treated unsaturated esters, acidsand ketones. Particularly valuable products may be obtained by reactingfrom 2 to 6 molds of at least one terpene hydrocarbon with at least onemole of phosphorus sulfide, especially P285. Particularly good resultsare secured by the employment of the products obtained by reacting about3 to 5 moles of pinene and/or turpentine with one mole of P285 for about1 to 6 hours, preferably about 4 hours, at about C. to (3., preferablydiflerent organic metal, especially a Mendeleef Periodic (e) Compoundsin which the C=S group is included in a ring structure, e. g. a

Thio-qumone Thio-naphthaquinones Thio-anthraquinone Thio-phthalicanhydride Thio-diphenic anhydride Diphenylene thioketone(thio-fluorenone) Thio-camphor (1') Carbon bisulfide 4. Compounds inwhich the -S radicle forms a part an organic 5. Sulfur atom attached inthe form of an inorganic radicla, e. g.

Thio-arsenite Thio-phosphite Tri-thio-Iauryl phosphite Thio-phosphateThio-sulionic acid, and esters and salts Thio-sulfinic acid, and estersand salts B Sulfur attached to molecule through means of some otheratom, i. e.,

the form of an inorganic radicle, e. g.

Thio-arsenate Thio-phosphate Thio-suliate Thio-sulfite Sulfate SulfiteThio-sulionate Of the organic sulfur compounds which do not have stableanalogous oxygen counter parts are those included in the followingtable:

Sulionic acids, and esters and salts of them Sulfinic acids, and estersand salts of them Bulienic acids, and esters and salts of themPolysulfides, containing the Sn radlcle, notably 1.

Alkyl polysulfides, e. g.,

Dioutyl disulfide Dibutyl trisulfide Dibutyl tetrasulfide Diamyldisulfide Diamyl trisulflde Dilauryl disulfide Dilauryl trisulfideCyclohexyl disulfide 2. Aryl polysulfides, e. g.

Diphenyl disulfide Diphenyl tnsulfide Chlor diphenyl trisulfideDinaphthyl disulfide 3. Aromatic substituted aliphatic polysulfides, e.g.

4. Mixed alkyl-aryl polysulfides, e. g.

5. Higher polysulfides, e. g. those formed from the above (or from Amylbenzyl disulfid Amyl benzyl trisulfide sulfides) by the addition of anS- group or groups.

Organic halogen compounds Halogenated aliphatic hydrocarbonsPentachloroethane Heptachloropropane Hexachlorobutadiene Chlorinatedneohexane containing 75% chlorine Chlorinated diisobutylene containing60% chlorine Chlorinated kerosene containing 45% chlorine Chlorinatedhexadecane containing 55% chlorine Chlorinated octadecane containing 50%chlorine Chlorinated eicosane containing 50% chlorine Chlorinateddocosane containing 50% chlorine Chlorinated ioots oil containing 40%chlorine Chlorinated mineral oil containing 40% chlorine Chlorinatedparafiin wax containing 40% chlorine Chlorinated petrolatum containing40% chlorine Halogenated aliphatic acids Dichlorostearic acidDichlorolauric acid Dichloropalmitic acid Halogenated aliphatic estersAlkyl dichlorolaurates Alkyl dichloropalmitates Alkyl dichlorostearatesHalogenated aromatic compounds Dichlorobenzene TrichlorobenzeneDichloronaphthalene lrichloronaphthalene PolychloronaphthalenoaHexachlorodiphenyl other Hexachlorodiphenyl sulfideHexachlorohenzophenone Specific examples of oil-soluble organicphosphorus acids which may be used in the practice of this inventioninclude the following:

Organic phosphorus compounds Dithiophosphoric acids Diamyldithiophosphoric acid Dihexyl dithiophosphoric acid Diheptyldithiophosphoric acid Dioctyl dithiophosphoric acid Dinonyldithiophosphorlc acid Didecyl dithiophosphoric acid Didodecyldithiophosphoric acid Ditetradecyl dithiophosphoric acid Dihexadecyldithiophosphoric acid Dioctadecyl dithiophosphorlc acid Di(parafiin wax)dithiophosphoric acid D1e1cosyl dithiophosphoric acid Dipentenyldithiophosphoric acid Dioctenyl dithiophosphoric acid Didecenyldithiophosphoric acid Dihexadecenyl dithiophosphoric acidDi(methyl-benzyl) dithiophosphoric acid Di-Eoctylbenzyl)dithiophosphoric acid Diphenyloctadecyl) dithiophosphoric acidDi-(xenylhexyl) dithiophosphoric acid Di-(phenoxyoctyl) dithiophosphoricacid D i-(butoxy-ethyl) dithiophosphoric acid B s-(3,5-dichloro-n-octyl)dithiophosphoric acid B1s-(2,6-dibromo-n-decyl) dithiophosphoric acidDicyclopentyl dithiophosphoric acid Bis-(dnncthylcyclopentyl)dithiophosphoric acid Dicyclohexyl dithiophosphoric acidDi-(methyl-cyclohexyl) dithiophosphoric acid Di-(isopropylcyclohexyl)dithiophosphoric acid Bis-(dnsobutylcyclohexyl) dithiophosphoric acidDmaphthenyl dithiophosphoric acid di (hydroabietyl) dithiophosphoricacid Dicyclopentenyl dithiophosphoric acid Di-(methylcyclohexenyl)dithiophosphoric acid Diabietyl dithiophosphoric acid Di-(tert-amyl-phenyl) dithiophosphoric acid Di-(2,4-di-tert-amyl-phenyl)dithiophosphoric acid Di-(paraffin wax-phenyl) dithiophosphoric acidDi-(lauroxyphenyl) dithiophosphoric acid Di-(caprylxenyl)dithiophosphoric acid Methyl octadecyl dithiophosphoric acid Butyl hexyldithiophosphorlc acid Isopropyl sec-amyl dithiophosphoric acidMonothiophosphoric acids Diheptyl thiophosphoric acid Dioctylthiophosphoric acid Dinonyl thiophosphoric acid Didodecyl thiophosphoricacid Dihexadecyl thiophosphoric acid Dioctadecyl thiophosphoric acidDi-(parafiin wax) thiophosphoric acid Dihexenyl thiophosphcric acidDidecenyl thiophosphoric acid Dihexadccenyl thiophosphoric acidDiphenethyl thiophosphoric acid Di-(butyl-benzyl) thiophosphoric acidDi-(octadecylphenyl) thiophosphoric acid Diphenoxydecyl thiophosphoricacid Di-(butoxyphenyl) thiophosphoric acid Di-(nitrophenyloctyl)thiophosphate acid Dicyclopentyl thiophosphoric acid Dicyclohexylthiophosphoric acid Di-(mcthyl-cyclohexyl) thiophosphoric acidThiophosphoric acid Dinaphthenyl thiophosphoric acid Dicyclohexenylthiophosphorlc acid Butyl hexyl thiophosphoric acid Amyl cyclohexylthiophosphate acid Isopropyl cyclohexyl thiophosphoric acid Phosphoricacids Dihexyl phosphoric acid Dioctyl phosphoric acid Didecyl phosphoricacid Diundecyl phosphoric acid Didodecyl phosphoric acid Dloctadecylphosphoric acid Dihexonyl phosphoric acid Dioctenyl phosphoric acidDidecenyl phosphoric acid Dioctadecenyl phosphoric acid Dicyclopentylphosphoric acid Dicyclohexyl phosphoric acid Di-(methylcyclohexyl)phosphoric acid Dicyclopentenyl hosphoric acid Dlcyclohexenyl p osphoricacid Di-(methyl-cyclohexenyl) phosphoric acid Di-(phenylbutyl)phosphoric acid Di-(naphthylethyl) phosphoric acidDi-(chlorophenyloctyl) phosphoric acid Di-(propylphenyl) phosphoric acidDi-(methyl-naphthyl) phosphoric acid Methyl decyl phosphoric acid Ethyldodccyl phosphoric acid Ethyl methylcyclohoxyl phosphoric acid Dithiohosphinic acids Di exyl dithiophosphinic acid Dioctyl dithiophosphinicacid Dinonyl dithlophcsphinic acid Ditetradecyl dithiophosphinic acidDidecenyl dithiophosphinic acid Dihexadecenyl dithiophosgillixilnlc acidDicyclohexyl dlthiophosp 0 acid In addition to theabovespecificexamplesof phosphorus acids, the metal salts of.eachsuc'hiacid maybe regarded also as further specificexarnp-lesofmaterials wbich may be used as starting materialsin the,praeticeto'fthis invention.

While the metal complexes of the present invention find their widestapplication in the;preparation ofllubricants intended for usein'fthe.crankcases roflintern'al com- 2gv bustion engines, they are alsouseful-in the preparation, as above indicated, ofimproveduextremegpressurellubricants. In addition to :these particularapplications,' 'theamet-al complexes of this inventionlmay also beuse'clin thepreparation of improved'lubricants forspecialized uses, such5 as jet aviation, topcylinder, steamzcylinden-steamlocomotivumihaymarggasengine,:refrigeratingmachine, hydraulic,compressor, turbine, spindle, and torque converter lubricants.

The lubricating oil base in :which the metal complexes t of the presentinvention and, optionally, certain additional improving agents "areincorporated may be of synthetic, vegetable, animal, or mineral origin.Because of their low cost, availability, and desirable properties,.themineral oils, i. e, those derived from petroleum, find the widestapplication intlre 'Itibticantfield.

This invention as heretofore described also relates to various types.of-fllubricant improving agents and lubrieating compositions. There is,at the present time, sundry mineral "oils, .each .best .suited from thestandpoint of viscosity and other properties for-different uses andenvironments. The oil base oftatlubricating composition of the presentinvention designedvfor'a particular use and enviornment will preferablytcontpriselallubricating oil having the characteristics now-Wellrecognized as bestsuitedfor such useand environment.

In the following tables, particular characteristics of refined minerallubricating oils best suited for 'many types of use and climatearedisclosed.

[The -.-actual Mpper limit of preferred viscosity index is infinite formost uses. The values given-in'the following tables indicate the presentcommercial maximum-values.

: Grankcase Typeiotf Climate Jet Aviation Top Cylinder :Steam .GyltnderGasoline .Dlesel Aviation Arctic k Preferred viscosity range 1 GHOFIO"F-... 5045g/100" 'F i 80120/2l0F. Flash pt. preferably no lower the. 300F 340 275 400 F. Pour pt. preferably no higher than 50 F -50 F .0 F

Temperate Preferred viscosity range 1 Flash pt. preferably no lower thanFour pt. preferably no higher than--.

Tropical l Expressed in Sayboltzflntverselsecohds at indicatedtemperature.

50150/100 F. i100-190/210 F. 300 F i500 -F su F.

man o 210 F. I =500 1*.

I Refrigerating Compressor Type of Climate Steam'Loeomo Gas Engine tiveI Machine Temperate Preferred viscosity range 1 "+00/210:F '50-'70/210F- -801210" F-.." BG ISgJ-IOOQ'E "125 300/l00F 200-600/100 F. Flash pt.preferably no lower than- :375 Fm- 350 is 375 F- 325 325? 350 l Pour pt.preferably no higher-than--- 0F "0 F 0 F 25 F .i =-0 F' 10F.

Tropical Preferred viscosity range L..- 3560 210-'F..--. '50-70/210"FL--- 40-80 210 F-.. -180/100" F 200l.000/ F..- 300-600/100 F. Flash pt.preferably no lowerthan- 375?. "3509i 375 350 F 360 F 350" 1. Pour pt.preferably no higher than 20F '15? E F --25 F Preferred V. I. (Dean andDavis) 35-120 354.20 I

1 Expressed in Saybolt Universal seconds'at; indicated temperature.

Klein. Type oi Climate Turbine Spindle Torque Converter AutomotiveIndustrial Arctic Preferred viscosity range 1 120-500/100" F...--35-100I100 F 20-80%;100 F 30-1,000/210 F. Flash pt. preferably no lowerthan. 375 F 275 F 275 30 300 F. Pon. pt. preferably no higher than 20 F.50 F -50 F 10 F.

Temperate I Preferred viscosity range 1 125500/100 F.---. 7040101100" F30-250/100 F 50140/210 F 502,000/210 F. Flash pt. preferably no lowerthan 400 F 275 300 F 325 F 325 F. Pour pt. preferably no higher than F F-30 F 0 F 20 F.

Tropical Prz'ferred viscosity range 1 125-500/100 F....- 150300/100F-...- 30 -301100 F 80 2001210 F 80-2,000/210 F. Flash pt. preferably nolower than 400 300 F 300 350 F 326 F. Pour pt. preferably no higher than20 F F 0 F F Preferred V. I. (Dean and Davis)-- 85-120 75-120 100-16075-120 -120.

1 Expressed in Saybolt Universal seconds at indicated temperature.

As indicated earlier, our metal complexes find their widest applicationin the preparation of lubricants intended for use in the crankcases ofinternal combustion engines, particularly in combination with otherimproving agents such as, in the preferred instance, dithiophosphatesalt-esters and/or phosphorussulfide treated unsaturated organicmaterials.

It is common practice in the lubricant additive industry to prepare aliquid, homogeneous concentrate containing one or more separateimproving agents and, optionally, a minor proportion of a mineral oil,preferably one of low viscosity. Such liquid concentrates dissolve morereadily in lubricating oil bases than do solid improving agents and, inaddition, minimize the problems usually associated with the processing,handling, and transportation of solid materials.

Thus the present invention contemplates not only the preparation offinished lubricants containing the metal complexes of our invention, butalso the preparation of lubricant improving agents, i. e. concentrates,which when dissolved in suitable lubricating oil bases will yieldfinished lubricants containing our metal complexes, and,

optionally, such other improving agents as are desired.

From an examination of the specification it will be noticed that ourmetal complexes vary widely in metal content, such metal content usuallybeing expressed, for convenience, as percent metal sulfate ash. As amatter of actual practice in the compounding of lubricants from ourmetal complexes, we have found that the amount of metal in combined formin the lubricant due to the presence of our complex is the criticalfactor to be considered. Since it has been shown that our metalcomplexes may differ very substantially in metal content, it followsthat in the preparation of a lubricant having a certain fixed proportionof metal due to our complex, one would use less of a metal complex ofhigh metal content than a similar metal complex of lower metal content.To illustrate this point more specifically, 10 parts by weight of acomplex of sulfate ash content dissolved in,90 parts by weight oflubrieating oil would yield a lubricant having the same metal content asone prepared by dissolving 40 parts by weight of a complex of 10%sulfate ash content in 60 parts by weight of lubricating oil.

It becomes apparent then that we can properly define the amounts of ourmetal complexes desirably present in lubricant improving agents, andlubricants only in terms of metal content or a proportional equivalentthereof, for example, metal sulfate ash content. Furthermore, it shouldbe pointed out that the desirable range of such metal or metal sulfateash content will difier substantially in going from one metal complex toa complex of'a difierent metal. This situation exists because differentmetals have different chemical combining weights,

saturated organic materials and are perforce present in different weightpercentages in complexes of our invention wherein the organic acid andpromoter material have been fixed both as to identity and amount.

As a consequence of a large number of tests performed on lubricantscontaining metal complexes of our invention, we have been able todetermine the operable ranges of metal content and metal sulfate ashcontent (due to the presence of our complexes) for both lubricantimproving agents and finished lubricants.

RANGES FOR WEIGHT PERCENT OF METAL SULFATE A wide variety ofoil-soluble, phosphorusand sulfurbearing organic materials are availableand are preferred for use in combination with our oil-soluble, metalcomplexes in preparing lubricant improving agents and lubricants.

By this statement we do not mean that all oil-soluble,phosphorus-and-sulfur-bearing organic materials are of equal eflicacyfor use in lubricant compositions. Some are more effective than others;for example, dithiophosphate salt-diesters and phosphorus sulfidetreated un (especially Pass-treated terpene hydrocarbons) have beenfound to be of particular utility.

By way of illustration, a numberof oil-soluble,phosphorus-and-sulfur-bearing organic materials are given, one or moreof which may be used along with our metal complexes in producinglubricant compositions:

I. Esters and salt-esters of inorganic thioacids of phosphorus, forexample (1) Esters of thiophosphorus acids, e. g.:

S-n-octyl monothiophosphite S S-dl-n-hexyi dithiophosphlte Tri-amyltrithiophosphite Laury] dicthyi trithiophosphite 0,0-di-n-hexylmonothiopbosphlte 0,S-di-n'octyldithiophosphlte Di-lauryltrithiophosphlto S-cetyl monothiophosphito (2 Salt-esters ofthiophosphorons acids, a. g.:

Barium S-oetyi monothiophosphite Strontium 0,S- dilauryl dithiophosphlteCalcium di-lauryl trithiophosphite Zinc S-octadccyl monothiophosphiteCopper 8,8-dl-decyl dithiophosphite ALCOHOLS AND MERCAPTANS Analysis ofReaction Product Example No. Organic Material Mols Additional ReaotantMols Reagent Mols Percent Percent Sulfur Phosphotons Capryl Alcohol 6OleioAcid 2 P481 1 12.2 6.4 4 1 1.7 2.5 6 1 8.7 6.2 do 8 1 5.4 4.6Sulfurized Oleyl Alcohol 3 1 9.1 2.0 Amyl Mercaptan 3 1 29.2 9.5

ACIDS AND ESTERS Oleic Acid 8 P481 1 5.9 4.4

do 8 P483 1 0.9 0.93

4 P451 1 8.5 3.6 8 P487 1 3.9 1.6 8 P451 1 6.9 3.6

SPECIFIC EXAMPLES OF LUBRICANT IMPROV- ING AGENTS AND EMPLOYING METALCOM- 25 Composition (weightpemm) Lubricant PLEXES OF THE PRESENTINVENTION Number Certain oil-soluble phosphorus-and-snlfur-bearing or-Percent ponent ganic materials used in many of the lubricantcompositions illustrated herein are designated as follows (unless 3g:61) 2 25 9 g ng r ag o i l I 2 otherwise stated, percentages given arein weight-percent 4 0:23 improving agent A. p e of total improvingagent): 8: 8g ig gg j fig 25832 97. i3 SAt 130 mirlleral oliil.

Improving Description 5 (022) ir n ios in g ag n t Af Agent 1. improvingagent B. 96. 3g. (0 sA E so mn iemi g.

. 1. .25 me a comp ex 0 xample 2.

A product prepared by reacting about 4 moles of turpentine with 1 moleof P255 for about 4 hours at about 140 C; 6 gg fi igzg 2 2E:

61% solution in low viscosity mineral oil. 44 ilngrovin a ent D B zincdi-(fi-methyl-see-amyl) dilthliirphosphate; 44% solu- 9200 SAE 30 i ionin ow viscosi y minera 0' O mixture of 60 mole-percent zinc di(4-methyl-sec-amyl) 7 (0-82) fi i'igg g i f dithiophosphate andmole-percent zinc di-isopropyl 4O 98 improving dithiophosphate; 40%solution in low viscosity numeral 92 imgroving ggg D ba ir iiim salt ofthe mixed dithiophosphate diester obzg g tained by treating a mixture ofl-methyl-sec-amyl, im g g g i p n-hexyl, and capryl alcohols (3, 2, and3parts by weight, 98 nt respectively) with P185; 39% solution inlow-viscosity imgroving aggnt D mum] 94. a2 sea 30 mineral oil.

1. 47 prigrlart viscositfy index improver. m. i t For each of thespecific lubricants shown hereinafter, 9 5 (0 38) ini pi 'osiiig n iixampled the composition of the corresponding lubricant improving 2i lagent can be discerned by considering the weight percent- 95:28 .5; 30

ages of the separate improving agents as parts by weight. g; (0 32) g ggg ggg ll engl'ovel.

For example, the lubricant improving agent correspond- 0 improving agentp ing to lubricant No. 1 would consist of 1 part by Weight 8.22 32 B ofimproving aglent B, plus 5 paiits by weight 02 the corltli- 95:79 sailzotmineraltoil; d

p 6X Of Examp 6 1 (01 0.71 SU fate ash part y weig t 0. 99 pr1or arVlSCOSl yin ex improver.

1.75 0.31 metal com 1 x of E 4, thereof). If the separate improvingagents do not them- 55 11 improving agent A.

selves contain a proportion of mineral oil, some may be 822 gggigzlgg352% 8- added, if necessary, to secure a fully liquid, multi-com- 96:35SAE 40 mineraloi]:

ponent concentrate as discussed earlier 1n the section H2 (0-33) figasgg e g f a ple 4.

regarding improving agent concentrates. improving agent The values inparentheses in the percent column 2-32 iiz zg ggsg gbelow give thepercent of metal sulfate ash present in 3115 0,45 metal complex ofExample 5.

the lubricant imparted by the amount and kind of metal lggggzi ggigcomplex employed therein. improving agent 1 96. 08 SAE 40 mineral oil.

2. 12 (0. 3) metal complex of Example 5.

Lub t Composition (weight percent) 14 $4 35333; 3.523% g.

H 8.11 Num ber 0. 46 impiigoving agent D. Percent Component 94. 97 SA 30mineral oil.

3. 4 (0. 48) metal complex of Example 5. 0.49 improving agent A. 94. 0SAE 30 mineral oil. 1.14 improving agent 0.

1 ?.g (0.71) metal complex oillsixample 1. 94 44 s ll ugr fi p t i -g ogrn gent.

. LID T0 in 8 8D 90 0 S153 5 0 u lin etal oil. 3. 38 (0. 62) metalcomplex of Example 6.

2 8.8 (1.14) metal cp m plex (ifgxample 1. 8. 2 35 225 kgg e r t t.

9 52 83E133?) m iiigg l 011: i 0: 92 improving agent I): 3 338 fi iii int f iii (1 83) ii i ofitiii tii'm e o 0: 98 imgroving agent 0: 0.5 zincdi-lauryl dithiophosphate.

0. 92 improving agent D. 0. 6 P and 8 bearing product of Example 11.

Composition (weight percent) Number Percent Component SAE 10 mineraloil.

metal complex of Example 6. magnesium di-n-octyl dithiophosphatc... Pand S bearing product, of Exzimplo 33. SAE 10 mineral oil.

metal'compl x of Example 7.

trinrnyl trithiophosphite.

P and S bearinc product of Exznrple l5. SAE 20 mineral oil.

metal complex of Example 7.

metal complex of Example 6.

trilauryl trithiophosphate.

P and S bearing product of Example 27. SAE 20 mineral oil.

metal complex of Example 7.

calcium di-rnrlecyl dithiophosphatc.

P and S hem-inc product of Example SAE 20 mineral oil.

metal complex of Example 8.

zinc di-(lauryl-phenyl't dithiophosphii P and S nearing product ofExample 3.3. SAE 20 mineral oil.

metal complex of Example 8.

barium carbonate complex of Example 7 cobalt di-capryl dithiophosphnte.

SAE 20 mineral oil.

metal complex of Example 8.

P and S bearing product of Example 38. SAE 30 mineral oil.

metal complex of Example 9.

improving agent 0.

SAE 30 mineral oil.

metal complex of Example 9.

nickel di-octadecyl dithiophosphate.

P and S bearing product of Example 19. SAE 30 mineral oil.

metal complex of Example 9. tri-(tert-butyl-phenyl) dithiophosphate. Pand S bearing product of Example 24. SAE 30 mineral oil.

metal complex of Example 10.

P and S bearing product of Example 39. SAE 30 mineral oil.

metal complex of Example 10. improving agent A.

SAE 30 mineral oil.

metal complex of Example 10. improving agent 0.

SAE 30 mineral oil.

metal complex of Example 10. zinc di-(methyl-cyclohexyl) :0 copulpoowgppucaccpaonc H H N! v v 0.2 (0.055) 1.5 81.0 15.0 (4.1) 31 2.0dithiophosphate. 2.0 P and S bearing product of Example 28.

1 2 parts per million.

Other modes of applying the principle of the invention may be employed,change being made as regards the details described, provided thefeatures stated in any of the following claims, or the equivalent ofsuch, be employed.

I therefore particularly point out and distinctly claim as my invention:

1. A process which comprises preparing and mixing a mass in which,211250 0., at least 50% of the total mass is in the liquid state, and inwhich mass the active componcnts consist of: A, at least one oil-solubleorganic acid compound; B, at least one organic metal compound derivedfrom a metal-free organic compound having: (a) an ionization constant inWater of at least about 1X10- at about 25 C.; (b) a Water solubility at50C. of at least about 0.0005%;'and (c) in saturated aqueous solutionsat about 25 C. a pH of not greater than about 7, the relative amounts ofA and B used being in the range of from about one equivalent of A toabout 10 equivalents of B to about 10 equivalents of A to about oneequivalent of B; C, Water, in an amount equal to at least about onetcnthmole per mole of B; maintaining the mass at a tempcraturo and for aperiod of time sufllcient to drive off substantially all free water andwater of hydration which may be present; and then treating the mass withan acidic material of which the ionization constant is higher than theionization constant of the organic compound from 3. The proccss'of claim1 further characterized in that component A is a. phosphorus acidcompound.

4. The process of claim 1 further characterized in that component A is athiophosphorus acid compound.

5. The process of claim 1 further characterized in that component A isat least 1 sulphur acid compound and at least 1 phosphorus acidcompound.

6. The process of claim 1 further characterized in that component A isat least 1 sulphur acid compound and at least 1 thiophosphorus acidcompound.

7. The process of claim 1 further characterized in that component A isat last lsulph'onic' acidcompound.

8. The process of claim 1 further characterized in that component A isat least 1 barium salt of an oil-soluble organic acid.

9. The process of claim 1 further characterized in that component Ais'thc barium salt of at least 1 sulphur acid.

10. The process of claim 1 further characterized inthat component A isthe barium salt of atlcast 1 phosphorus acid.

11. The process of claim 1 further characterized in that component A i'sthe barium-salt of at least l'thiophos phorus acid.-

12. The process of claim 1 further characterized in that component A isa mixture of the barium salts of at least 1 sulfur acid and the bariumsalts of at least one phos phorus acid.

13. The process of claim 1 further characterized in that component A isa mixture of the barium salts of at least one sulfur acid and the bariumSalts of at least one thiophosphorus acid.

14. T he process of claim 1 further characterized in that component A isat least one barium sulfonate.

15 The process of claim 1 further characterized in that component A is amixture of at least one barium sulfonatc and the barium salts of atleast one phosphorus acid.

16. The process of claim 1 further characterized in that component A isa mixture of at least one barium sulfonatc and the barium salts of atleast one thiophosphorus acid.

17. The process of claim 1 further characterized in that component B isthe metal salt of a phenolic compound.

18. The process of claim 1 further characterized in that component B isthe metal salt of a phenol.

19. The process of claim 1 furtherchar'actc'rizcd in that component B isthe metal salt of a hydrocarbon substituted phenol in which thehydrocarbon substituents have not more than 16 carbon atoms.

2.0. The process of claim 1 further characterized in that component B isthe metal salt of an alkyl phenol.

21. The process of claim 1 furthcr'charactcrizcd in that component B isthe rntal sa'lt ofan cnolic compound.

22. The process ofclaim '1 further characterized in that the processistrcated with C02 in amounts sufilcicnt to liberate a substantialproportion of said organic compound of componnt BJ 23. The process'ofclaim 1 further characterized in that the component A is a mixture ofpetroleum mahogany sulphonic acid compounds and oil soluble alkylaromatic sulphonic acid compounds. 7

24. The process of claim 1 furthcrcharac tcriz ed in that the processmass is strippcd'of said liberated organic compound of component B.

25. The process of claim 1 further characterized in that said processmass is treated with CO2 in amounts sufficient to libcrateasubst'antialproportion of said organic compound of component'B, and saidliberated portions of said organic cornpoundofcomponent B a'rcs'trippcdfrom the process mass. V

26. A product in accordance with the process of claim 1..

(References on following page) References Cited in the file of thispatent UNITED STATES PATENTS 4 v. 38 Assefi? et 211. Nov. 4, 1952Assefl? et a1 Nov. 4, 1952 Asseff et a1 Nov. 4, 1952 Asseff et a1. Nov.4, 1952

1. A PROCESS WHICH COMPRISES PREPARING AND MIXING A MASS IN WHICH, AT50*C., AT LEAST 50% OF THE TOTAL MASS IS IN THE LIQUID STATE, AND INWHICH MASS THE ACTIVE COMPONENTS CONSISTI OF: A, AT LEAST ONEOIL-SOLUBLE ORGANIC ACID COMPOUND; B AT LEAST ONE ORGANIC METAL COMPOUNDDERIVED FROM A METAL-FREE ORGANIC COMPOUND HAVING: (A) AN IONIZATIONCONSTANT IN WATER OF AT LEAST ABOUT 1X10-10 AT ABOUT 25*C., (B) A WATERSOLUBILITY AT 50*C. OF AT LEAST ABOUT 0.0005%; AND (C) IN SATURATEDAQUEOUS SOLUTIONS AT ABOUT 25*C. A PH OF NOT GREATER THAN ABOUT 7, THERELATIVE AMOUNTS OF A AND B USED BEING IN THE RANGE OF FROM ABOUT ONEEQUIVALENT OF A TO ABOUT 10 EQUIVALENTS OF B TO ABOUT 10 EQUIVALENTS OFA TO ABOUT ONE EQUIVALENT OF B; C, WATER, IN AN AMOUNT EQUAL TO AT LEASTABOUT ONETENTH MOLE PER MOLE OF B; MAINTAINING THE MASS AT A TEMPERATUREAND FOR A PERIOD OF TIME SUFFICIENT TO DRIVE OFF SUBSTANTIALLY ALL FREEWATER AND WATER OF HYDRATIO WHICH MAY BE PRESENT; AND THEN TREATING THEMASS WITH AN ACIDIC MATERIAL OF WHICH THE IONIZATION CONSTANT IS HIGHERTHAN THE IONIZATION CONSTANT OF THE ORGANIC COMPOUND FROM WHICH WASDERIVED COMPONENT B AND IN AMOUNTS SUFFICIENT TO LIBERATE A SUBSTANTIALPROPORTION OF SAID ORGANIC COMPOUND OF COMPONENT B.